Process for Forming an Electrolytic Capacitor Having a Higher Cap Recovery and Lower ESR

ABSTRACT

Provided is an improved capacitor formed by a process comprising: providing an anode comprising a dielectric thereon wherein the anode comprises a sintered powder wherein the powder has a powder charge of at least 45,000 μFV/g; and forming a first conductive polymer layer encasing at least a portion of the dielectric by applying a first slurry wherein the first slurry comprises a polyanion and a conductive polymer and wherein the polyanion and conductive polymer are in a weight ratio of greater than 3 wherein the conductive polymer and polyanion forms conductive particles with an average particle size of no more than 20 nm.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of pending U.S. patentapplication Ser. No. 15/379,729 filed Dec. 15, 2016 which, in turn,claims priority to expired U.S. Pat. Appl. No. 62/267,707 filed Dec. 15,2015. U.S. patent application Ser. No. 15/379,729 is acontinuation-in-part application of U.S. patent application Ser. No.14/743,195 filed Jun. 18, 2015, now U.S. Pat. No. 9,941,055 issued Apr.10, 2018, which is, in turn, a continuation-in-part application of U.S.patent application Ser. No. 13/777,769 filed Feb. 26, 2013 now U.S. Pat.No. 9,312,074 issued Apr. 12, 2016, which in turn, claims priority toexpired U.S. Provisional Patent Appl. No. 61/603,635 filed Feb. 26, 2012all of which are incorporated herein by reference. This application isalso a continuation-in-part of pending U.S. patent application Ser. No.15/595,137 filed May 15, 2017 which claims priority to expired U.S.Provisional Patent Application No. 62/338,778 filed May 19, 2016 both ofwhich are incorporated herein by reference.

BACKGROUND

The present invention is related to an improved method of forming asolid electrolytic capacitor and an improved capacitor formed thereby.More specifically, the present invention is related to improvedconductive polymer slurries and methods for improving capacitance andequivalent series resistance (ESR) of solid electrolytic capacitorsusing improved conductive polymer slurries.

The construction and manufacture of solid electrolytic capacitors iswell documented. In the construction of a solid electrolytic capacitora, preferably valve, metal serves as the anode. The anode body can beeither a porous pellet, formed by pressing and sintering a high puritypowder, or a foil which is etched to provide an increased anode surfacearea. An oxide of the valve metal is electrolytically formed to coverall surfaces of the anode and serves as the dielectric of the capacitor.The solid cathode electrolyte is typically chosen from a very limitedclass of materials, to include manganese dioxide or electricallyconductive organic materials such as polyaniline, polypyrrole,polythiophene and their derivatives. Solid electrolytic capacitors withintrinsically conductive polymers as the cathode material have beenwidely used in the electronics industry due to their advantageously lowequivalent series resistance (ESR) and “non-burning/non-ignition”failure mode. In the case of conductive polymer cathodes, the conductivepolymer is typically applied by either chemical oxidationpolymerization, electrochemical oxidation polymerization or spraytechniques with other less desirable techniques being reported.

The anode body is typically a porous structure because the porosityincreases the surface area which increases capacitance for a givenvolume. The conductive cathode layer often comprises conductivematerials such as the conductive polymer, carbon and silver layers forconnection with terminals. It is extremely important for the porousanode surface to be sufficiently covered and in close contact with theconductive cathode layer and it is particularly preferred that the poresbe completely impregnated with conductive cathode layer to achievetargeted capacitance. In a manufacturing process to produce conductivepolymer-based valve metal capacitors the valve metal powder, such astantalum, is mechanically pressed into anodes that are subsequentlysintered to form porous bodies. The anodes are anodized to apre-determined voltage in a liquid electrolyte to form a dielectriclayer onto which a cathode layer of conductive polymer is formed. Theconductive polymer is then coated with graphite and a metal layerfollowed by assembling and molding into a finished device.

The major drawback of conductive polymer capacitors, regardless of thetypes of conductive polymers employed, is their relatively low workingvoltage compared to their MnO₂ counterparts. The polymer capacitors havereliability issues, to varying degrees, when the voltage rating exceeds25V. This is believed to be caused by the relatively poordielectric-polymer interface, which has poor “self-healing” capability.The ability to withstand high voltage can be best characterized by thebreakdown voltage (BDV) of the capacitors. Higher BDV corresponds tobetter reliability. For reasons which were previously unknown, thebreakdown voltage of capacitors comprising conductive polymers has beenlimited to about 55V thereby leading to a capacitor which can only berated for use at about 25V. This limitation has thwarted efforts to useconductive polymers more extensively.

Tantalum capacitors with conductive polymer cathode gained commercialsuccess because of their low ESR and self-heating nature. They are oftenconstructed with at least two polymer layers: an internal polymer layerto fill up pores inside the anode body and an external polymer layer toprotect outside dielectric from the subsequently formed carbon andsilver layers. The internal conductive polymer layer is in directcontact with most available dielectric surface and is the main factorthat affects capacitance. The internal conductive polymer layer can beformed by either in-situ polymerization or by coating with preformedpolymer dispersion or solution. The in-situ polymerization approachoften yields higher capacitance and lower ESR. However, carrying outchemical reactions on dielectric is a complex process and can damage thedielectric. In addition, residual metal salts from the in-situpolymerization may cause undesirable performance loss such as highleakage and low breakdown voltage. In-situ polymerization is often runfor multiple cycles to fill up the pores of anode body. However, themore cycles are run, the more damage it will cause to dielectric, so itis desirable to reduce to number of in-situ polymerization cycles asmuch as possible and replace it with less harmful processes.

For capacitors used for high voltage applications, the preformed polymerapproach is more preferred. Applying preformed polymer reduces leakageand improves breakdown voltage, but with trade-offs. The most successfulpreformed polymer utilizing PEDOT and polystyrene sulfonic acid (PSSA)as the counterion is a dispersion comprising particles. Depending on thesize of the particles, it is often difficult to impregnate all the poresof the anode body, especially if the pores are small, and capacitancesuffers with incomplete impregnation. U.S. Pat. No. 8,058,135 teachesconductive polymer dispersion with an average particle diameter of 1-100nm. Numerous efforts have been made to prepare conductive polymerdispersion with lower average particle sizes or even completely solubleconductive polymer solution, however, these dispersion/solutions oftenhave shelf life issues or are not stable under heat or chemicalprocessing once applied. Existing soluble conductive polymers typicallysuffer from very low conductivity, which means higher ESR forcapacitors.

Preformed conductive polymer often has a much lower conductivity thanconductive polymer made via in-situ methods. For example, U.S. PatentNo. 9,514,888 teaches a conductivity of the conductive polymer of only483 S/cm even with DMSO addition. Even with such a high conductivity fora dispersion, the final ESR is still higher than the comparative exampleusing in-situ 3,4-polyethylene dioxythiophene (PEDOT). In-situ PEDOT'sconductivity can be as high as thousands of siemens/cm (S/cm). The ESRof polymer-based capacitors is considered directly related toconductivity of the cathode layer and higher conductivity is thereforealways desired for the conductive polymer dispersion.

In spite of the extensive research a need exists for materials andmethods which improves capacitance and ESR without adversely impactingother aspects such as leakage and BDV. An advancement in the formationof a cathode layer on solid electrolytic capacitors is provided herein.

SUMMARY OF THE INVENTION

It is an object of the invention to provide an improved solidelectrolytic capacitor.

It is another object of the invention to provide an improved method forpreparing a solid electrolytic cathode capacitor with improvedcapacitance and ESR.

These and other advantages, as will be realized, are provided a processfor forming an electrolytic capacitor comprising:

providing an anode comprising a dielectric thereon wherein the anodecomprises a sintered powder wherein the powder has a powder charge of atleast 45,000 μFV/g; and forming a first conductive polymer layerencasing at least a portion of the dielectric by applying a first slurrywherein the first slurry comprises a polyanion and a conductive polymerand wherein the polyanion and conductive polymer are in a weight ratioof greater than 3 wherein the conductive polymer and polyanion formsconductive particles with an average particle size of no more than 20nm.

Yet another embodiment is provided in an electrolytic capacitor. Theelectrolytic capacitor comprises an anode comprising a dielectricthereon. The anode comprises a sintered powder wherein the powder has apowder charge of at least 45,000 μFV/g. A first conductive polymer layerencases at least a portion of the dielectric wherein the firstconductive polymer comprises a polyanion and a conductive polymer. Thepolyanion and conductive polymer are in a weight ratio of greater than 3wherein the conductive polymer and polyanion are conductive particleshaving an average particle size of no more than 20 nm.

FIGURES

FIG. 1 is a schematic cross-sectional view of an embodiment of theinvention.

FIG. 2 is a flow chart representation of an embodiment of the invention.

FIG. 3 is a graphical representation of conductivity as a function ofthe weight ratio of polyanion to conductive polymer.

FIG. 4 is a graphical representation of capacitance (normalized) as afunction of the weight ratio of polyanion to conductive polymer.

FIG. 5 is a graphical representation of ESR (normalized) as a functionof the weight ratio of polyanion to conductive polymer.

DESCRIPTION

The instant invention is specific to a method of making a solidelectrolytic capacitor and a solid electrolytic capacitor made thereby.More specifically, the instant invention is specific to a solidelectrolytic capacitor with improved capacitance and ESR achieved by theuse of a slurry comprising a weight ratio of polyanion to conductivepolymer of greater than 3 and particles sizes of no more than 20 nm. Theslurry is applied to an anode prepared from a powder having a charge ofover 45,000 μFV/g. Surprisingly, the high ratio of polyanion toconductive polymer decreases the conductivity of the slurry which isindicated in the art to be detrimental for electrical properties. Thesynergistic effect realized with the high charge powder, and smallaverage particle size, provides for improvements in capacitance and ESRwhich is contrary to expectations in the art.

It now has been found that for a tantalum anode comprising a sinteredpowder wherein the powder has a specific charge of at least 45,000μFV/g, better capacitance and ESR could be achieved by using a firstslurry comprising conductive polymer and polyanion with a weight ratioof polyanion to conductive polymer of greater than 3 with an averageparticle size of no more than 20 nm. The improved electricalperformance, especially ESR of the capacitor is contrary to expectationsin the art since the higher ratio of polyanion is detrimental toconductivity. The art teaches the necessity of lower weight ratios toincrease conductivity of the slurry. U.S. Publ. Pat. Appl. 2015/0279503teaches the importance of utilizing a weight ratio of polyanion toconductive polymer of lower than 2 to improve capacitance. It is nowsurprisingly realized that with high specific charge, small particlesize and increased weight ratio of polyanion to conductive polymer aconductivity of less than 200 S/cm is preferable when utilized with ananode formed from high charge powder which is contrary to expectationsin the art.

The invention will be described with reference to the various figureswhich form an integral non-limiting component of the disclosure.Throughout the disclosure similar elements will be numbered accordingly.

An embodiment of the invention is illustrated in cross-sectionalschematic side view in FIG. 1. In FIG. 1, a capacitor, generallyrepresented at 10, comprises an anodized anode, 12, with an anode leadwire, 14, extending therefrom or attached thereto. The anode lead wireis preferably in electrical contact with an anode lead, 16. An optional,preferably in-situ formed, precursor conductive layer, 15, is formed onthe anodized anode and preferably the precursor conductive layer atleast partially encases a portion of dielectric of the anodized anode.Alternatively, the precursor conductive layer is formed by coating andcuring of a soluble conductive polymer solution. A first conductivepolymer layer, 18, and subsequent conductive polymer layer(s), 20, as acathode layer are formed sequentially on the precursor conductive layerand at least partially encase at least a portion of the first conductivelayer and form an encasement around at least a portion of thedielectric. As would be realized to those of skill in the art thecathode and anode are not in direct electrical contact in the finishedcapacitor. A cathode lead, 22, is in electrical contact with the cathodelayers. It is well understood that soldering a lead frame, or externaltermination, to a polymeric cathode is difficult. It has thereforebecome standard in the art to provide conductive interlayers, 23, whichallow solder adhesion. In many embodiments it is preferred to encase thecapacitor in a non-conductive resin, 24, with at least a portion of theanode lead and cathode lead exposed for attachment to a circuit board aswould be readily understood by one of skill in the art.

The optional precursor conductive layer comprises a conductive polymerpreferably formed by in-situ polymerization or coating and curing of asoluble conductive polymer. An in-situ formed conductive polymer ishypothesized to more effectively enter the interstitial portions of theporous anodized anode thereby forming an improved capacitor. Subsequentlayers are formed preferably by dipping into a slurry comprisingpre-polymerized conductive polymer with additional additives as will bemore specifically set forth herein. A soluble conductive polymer is aconductive polymer that completely dissolves in a solvent or solventmixture without detectable particles with below about 1 nm beingconsidered below typical particle size detection limits. The solvent forthe soluble conductive polymer can be water or organic solvents, ormixture of water with miscible solvents such as alcohol and nonhydroxypolar solvents such as dimethyl sulfoxide (DMSO), dimethylformamide(DMF), dimethylacetamide (DMAc), etc. A conductive polymer solutionpotentially can impregnate the pores of anodes as effectively asconductive polymers formed by in-situ methods and better than conductivepolymer dispersion with detectable particles. Neither in-situ conductivepolymer nor soluble conductive polymer contains polyanion dopants suchas polystyrene sulfonic acid. In many cases, soluble conductive polymerscontain self-doping functionalities. Examples of soluble conductivepolymers include conductive polymers of polyanilines, polypyrroles andpolythiophenes each of which may be substituted.

Particularly preferred conductive polymers includepoly(3,4-ethylenedioxythiophene),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulphonicacid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole),poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole),poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole),poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole),poly(3-methyl-4-carboxyethylpyrrole),poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole),poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene),poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene),poly(3-decylthiophene), poly(3-dodecylthiophene),poly(3-octadecylthiophene), poly(3-bromothiophene),poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene),poly(3-hydroxythiophene), poly(3-methoxythiophene),poly(3-ethoxythiophene), poly(3-butoxythiophene),poly(3-hexyloxythiophene), poly(3-heptyloxythiophene),poly(3-octyloxythiophene), poly(3-decyloxythiophene),poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene),poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene),poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene),poly(3,4-butenedioxythiophene), poly(3-carboxythiophene),poly(3-methyl-4-carboxythiophene),poly(3-methyl-4-carboxyethylthiophene),poly(3-methyl-4-carboxybutylthiophene), polyaniline,poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), poly(3-aniline sulfonate), and the like.

The first conductive polymer layer is formed by applying a first slurry,preferably by dipping, wherein the first slurry comprises a polyanionand a conductive polymer in a weight ratio of polyanion to conductivepolymer of greater than 3 to preferably no more than 10. While notlimited to theory, it is hypothesized that the polyanion rich firstslurry provides enhanced coating and therefore improves ESR of the finalcapacitor. More preferably the weight ratio is greater than 3 to morethan 6. The first conductive polymer layer may be applied from multipleapplications of the same slurry. For purposes of this disclosure thefirst conductive polymer layer is a layer formed by the first slurry andsubsequent conductive polymer layers are formed by a second slurrywherein each subsequent layer may have the same composition or adifferent composition.

The subsequent conductive polymer layers are formed by applying a secondslurry, preferably by dipping, wherein the second slurry comprises apolyanion and conductive polymer wherein the weight ratio of polyanionand conductive polymer is not particularly limited. It is preferablethat the subsequent conductive polymer layers have a weight ratio ofpolyanion to conductive polymer which is less than 3. A slurry having aweight ratio of polyanion to conductive polymer of less than 3 hashigher conductivity which is preferable for all but the first conductivepolymer layer.

An embodiment of the invention is illustrated in flow chart form in FIG.2. In FIG. 2, the method of forming a solid electrolytic capacitor ofthe instant invention is illustrated. In FIG. 2, an anodized anode isprovided at 32. An optional precursor conductive polymer layer is formedat 34 wherein the precursor conductive polymer comprises a conductivepolymer preferably without polyanion and is preferably formed by in-situpolymerization or by coating and curing of a soluble conductive polymersolution. The first conductive polymer layer may be formed by multipleapplications of the first slurry. A first conductive polymer layer isformed on the precursor conductive layer at 36 if present, preferably bydipping into a first slurry, wherein the first slurry is describedabove. After the first conductive polymer layer is formed, andpreferably cured, a subsequent conductive polymer layer is formed on thefirst conductive polymer layer wherein the subsequent conductive polymerlayer comprises polyanion and conductive polymer from a second slurry asdefined above. The subsequent conductive polymer layer optionallycomprises a crosslinker and particularly an amine crosslinker. Theapplication of additional subsequent polymer layers may be used ifdesired. It is preferable to apply at least one carbon containing layerand at least one metal containing layer on the final conductive carbonlayer, at 40, after which anode and cathode leads are attached to theanode and cathode respectively and the capacitor is optionally, butpreferably, encased at 42 and tested. In an embodiment the polyanion is,preferably polystyrenesulfonate.

In an embodiment the polyanion is preferably, a copolymer ofpolystyrenesulfonate and polystyrene.

In an embodiment the polyanion is a, preferably, random copolymercomprising groups A, B and C represented by the ratio of Formula A:

A_(x)B_(y)C_(z)  Formula A

wherein:A is polystyrenesulfonic acid or salt of polystyrenesulfonate;B and C separately represent polymerized units substituted with a groupselected from:-carboxyl groups;—C(O)OR⁶ wherein R⁶ is selected from the group consisting of:

-   -   an alkyl of 1 to 20 carbons optionally substituted with a        functional group selected from the group consisting of hydroxyl,        carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene,        alkyne, azide, phosphate, acrylate, anhydride and        -   —(CHR⁷CH₂O)_(b)-R⁸ wherein:        -   R⁷ is selected from a hydrogen or an alkyl of 1 to 7 carbons            and preferably hydrogen or methyl;        -   b is an integer from 1 to the number sufficient to provide a            molecular weight of up to 200,000 for the —CHR⁷CH₂O— group;            and        -   R⁸ is selected from the group consisting of hydrogen,            silane, phosphate, acrylate, an alkyl of 1 to 9 carbons            optionally substituted with a functional group selected from            the group consisting of hydroxyl, carboxyl, amine, epoxy,            silane, amide, imide, thiol, alkene, alkyne, phosphate,            azide, acrylate, and anhydride;            —C(O)—NHR⁹ wherein:    -   R⁹ is hydrogen or an alkyl of 1 to 20 carbons optionally        substituted with a functional group selected from the group        consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide,        imide, thiol, alkene, alkyne, phosphate, azide, acrylate and        anhydride;        —C₆H₄—R¹ wherein:    -   R¹⁰ is selected from:    -   a hydrogen or alkyl optionally substituted with a functional        group selected from the group consisting of hydroxyl, carboxyl,        amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,        phosphate, azide, acrylate and anhydride;    -   a reactive group selected from the group consisting of hydroxyl,        carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene,        alkyne, phosphate, azide, acrylate, anhydride and    -   —(O(CHR¹¹CH₂O)_(d)—R¹² wherein:    -   R¹¹ is a hydrogen or an alkyl of 1 to 7 carbons and preferably        hydrogen or methyl;    -   d is an integer from 1 to the number sufficient to provide a        molecular weight of up to 200,000 for the —CHR¹¹CH₂O— group;    -   R¹² is selected from the group consisting of hydrogen, an alkyl        of 1 to 9 carbons optionally substituted with a functional group        selected from the group consisting of hydroxyl, carboxyl, amine,        epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate,        azide, acrylate and anhydride;        —C₆H₄—O—R¹³ wherein:    -   R¹³ is selected from:    -   a hydrogen or an alkyl optionally substituted with a reactive        group selected from the group consisting of hydroxyl, carboxyl,        amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,        azide, acrylate, phosphate and anhydride;    -   a reactive group selected from the group consisting of epoxy,        silane, alkene, alkyne, acrylate, phosphate and    -   —(CHR¹⁴CH₂O)_(e)—R¹⁵ wherein:    -   R¹⁴ is a hydrogen or an alkyl of 1 to 7 carbons and preferably        hydrogen or methyl;    -   e is an integer from 1 to the number sufficient to provide a        molecular weight of up to 200,000 for the —CHR¹⁴CH₂O— group; and    -   R¹⁵ is selected from the group consisting of hydrogen and an        alkyl of 1 to 9 carbons optionally substituted with a functional        group selected from the group consisting of hydroxyl, carboxyl,        amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,        azide, acrylate, phosphate and anhydride; and        x, y and z, taken together are sufficient to form a polyanion        with a molecular weight of at least 100 to no more than 500,000        and y/x is 0.01 to 100; z is 0 to a ratio z/x of no more than        100; more preferably x represents 50-99%, y represents 1 to 50%        and z represents 0 to 49% of the sum total of x+y+z; even more        preferably x represents 70-90%; y represents 10 to 30% and z        represents 0 to 20% of the sum total of x+y+z.

In one embodiment the polyanion functions as a coating aid withinsufficient polystyrene sulfonic acid groups to function as anefficient counterion to the conductive polymer. In this instance it ispreferable that in the polyanion is represented by Formula A wherein xrepresents 1-40%, y represents 60 to 99% and z represents 0 to 39% ofthe sum total of x+y+z; even more preferably x represents 5 to 40%; yrepresents 60 to 95% and z represents 0 to 35% of the sum total ofx+y+z.

Particularly preferred polyanions include:

wherein b, x, y and z are as defined above.

The polyanion copolymers are preferably synthesized by a free radicalpolymerization method. By way of non-limiting example, different ratiosof salt of styrene sulfonic acid, to form component A of Formula A, andthe appropriate monomers for formation of components B and C of FormulaA, are polymerized in the presence of free radical initiator at hightemperature preferably ranging from 25° C. to 150° C. and under inertatmospheric condition.

The solvent in which the monomer(s) are to be dissolved is preferablywater. A water-soluble solvent may be used, or a mixture of water and awater-soluble solvent may be used. The water-soluble solvent is notparticularly limited. Examples of the solvent include acetone,tetrahydrofuran, methanol, ethanol, isopropanol, andN-methyl-2-pyrrolidone.

The polymerization initiator is not particularly limited, and may be,for example, a peroxide, or an azo compound. Examples of the peroxideinclude ammonium persulfate, potassium persulfate, hydrogen peroxide,cumene hydroperoxide, and di-t-butylperoxide. Examples of the azocompound include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), and 2,2′-azobisisobutyronitrile.The polyanion copolymer can be used directly without furtherpurification in the preparation of conductive polymer dispersion.Moreover, the polyanion copolymer can be purified, preferably bydialysis, precipitation, ultrafiltration or ion exchange method prior tothe preparation of conductive polymer dispersion.

The conductive polymer dispersion is preferably prepared in accordancewith U.S. Pat. No. 9,030,806 which is incorporated herein by reference.The preferred polymerization method uses a stator screen which providesa uniform droplet size resulting in preferred average polymer particlesizes below about 20 nm.

The inventive conductive polymer dispersion can be prepared by differenttechnologies. Conventional impeller mixing, rotor-stator high shearmixing, ultrasonic mixing, acoustic mixing and other mixing technologiescan all be used with their unique advantages. The inventive conductivepolymer dispersion is subjected to further processing to reduce itsaverage diameter, preferably to under 20 nm. For example, the dispersioncan be further homogenized by different methods such as high-pressurehomogenizer, higher shearing homogenizer, ultrasonic devices, acousticmixer, etc. The dispersion can also be subjected to purification andseparation such as dialysis and ultrafiltration to removenon-complexing/non-doping polyanions, separate different averageparticle sizes and different fractions of the dispersion. These postprocessing steps can improve capacitance, power cycling capacitancestability, ESR, impedance and other properties.

Conductive polymer dispersions having a lower, and controllable, averageparticle size can be prepared during polymerization, without additionalprocess steps, when the polymerization is carried out using a rotorstator mixing system with perforated screen stators preferably with holediameters below about 6 mm. The dispersion may be further processed orhomogenized to lower particle size.

The inventive conductive polymer dispersion can also be formulated bymixing with different additives to improve performance. Additives suchas silane coupling agents, crosslinking compounds especially epoxy andcarboxylic crosslinking compounds, sugar, alcohols, nonionic polyols orionic liquids can be added into the conductive polymer dispersion orapplied as a separate layer after the conductive polymer dispersion.When added as additives in the conductive polymer dispersion, thesenonconductive additive molecules may form complexes with the conductivepolymer and the conductive polymer complex, or particle, may consist ofthe extra insulative layer of compound in the conductive polymerparticles. Potential benefits of conductive polymer particles consistingof these insulative additives include better adhesion to adjacentlayers, better healing of the underlying dielectric layers and loweringthe work function of the cathode layer to help capacitance, ESR,leakage, breakdown voltage and anomalous charge behavior. The additivescan be added to the conductive polymer dispersion for all the multipledipping cycles or can be added for some of the dipping cycles.

Though not limited thereto, the present invention is particularlysuitable for use in forming conductive polymers of polyanilines,polypyrroles and polythiophenes each of which may be substituted. Thepreferred monomer for polymerization is shown as polymerized in FormulaB:

wherein:R¹ and R² independently represent linear or branched C₁-C₁₆ alkyl orC₂-C₁₈ alkoxyalkyl; or are C₃-C₈ cycloalkyl, phenyl or benzyl which areunsubstituted or substituted by C₁-C₆ alkyl, C₁-C₆ alkoxy, halogen orOR³; or R¹ and R², taken together, are linear C₁-C₆ alkylene which isunsubstituted or substituted by C₁-C₆ alkyl, C₁-C₆ alkoxy, halogen,C₃-C₈ cycloalkyl, phenyl, benzyl, C₁-C₄ alkylphenyl, C₁-C₄ alkoxyphenyl,halophenyl, C₁-C₄ alkylbenzyl, C₁-C₄ alkoxybenzyl or halobenzyl, 5-, 6-,or 7-membered heterocyclic structure containing two oxygen elements. R³preferably represents hydrogen, linear or branched C₁-C₁₆ alkyl orC²-C₁₈ alkoxyalkyl; or are C³-C⁸ cycloalkyl, phenyl or benzyl which areunsubstituted or substituted by C₁-C⁶ alkyl;X is S, N or O and most preferable X is S;R¹ and R² of Formula B are preferably chosen to prohibit polymerizationat the β-site of the ring as it is most preferred that only α-sitepolymerization be allowed to proceed; it is more preferred that R¹ andR² are not hydrogen and more preferably, R¹ and R² are α-directors withether linkages being preferable over alkyl linkages; it is mostpreferred that the R¹ and R² are small to avoid steric interferences.

In a particularly preferred embodiment the R¹ and R² of Formula B aretaken together to represent —O—(CHR⁴)_(n)—O— wherein:

n is an integer from 1 to 5 and most preferably 2;R⁴ is independently selected from hydrogen; a linear or branched C₁ toC₁₈ alkyl radical C₅ to C₁₂ cycloalkyl radical, C₆ to C₁₄ aryl radicalC₇ to C₁₈ aralkyl radical or C₁ to C₄ hydroxyalkyl radical, optionallysubstituted with a functional group selected from carboxylic acid,hydroxyl, amine, substituted amines, alkene, acrylate, thiol, alkyne,azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy,anhydride, silane, and phosphate; hydroxyl radical; or R⁴ is selectedfrom —(CHR⁵)_(a)—R¹⁶—, —O(CHR⁵)_(a)R¹⁶; —CH₂O(CHR⁵)^(a)R¹⁶;—CH₂O(CH₂CHR⁵O)_(a)R¹⁶, orR⁴ is a functional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene,thiol, alkyne, azide, sulfonic acid, benzene sulfonic acidsulfate, SO₃M,anhydride, silane, acrylate and phosphate;R⁵ is H or alkyl chain of 1 to 5 carbons optionally substituted withfunctional groups selected from carboxylic acid, hydroxyl, amine,alkene, thiol, alkyne, azide, epoxy, acrylate and anhydride;R¹⁶ is H or SO₃M or an alkyl chain of 1 to 5 carbons optionallysubstituted with functional groups selected from carboxylic acid,hydroxyl, amine, substituted amines, alkene, thiol, alkyne, azide,amide, imide, sulfate, SO₃M, amide, epoxy, anhydride, silane, acrylateand phosphate;a is integer from 0 to 10; andM is a H or cation preferably selected from ammonia, sodium orpotassium.

The conducting polymer is preferably chosen from polypyrroles,polyanilines, polythiophenes and polymers comprising repeating units ofFormula B, particularly in combination with organic sulfonates. Aparticularly preferred polymer is 3,4-polyethylene dioxythiophene(PEDOT).

Particularly preferred conductive polymers includepoly(3,4-ethylenedioxythiophene),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulphonicacid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole),poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole),poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole),poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole),poly(3-methyl-4-carboxyethylpyrrole),poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole),poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene),poly(3-hexylthiophene), poly(3-heptylthlophene), poly(3-octylthiophene),poly(3-decylthiophene), poly(3-dodecylthiophene),poly(3-octadecylthiophene), poly(3-bromothiophene),poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene),poly(3-hydroxythiophene), poly(3-methoxythiophene),poly(3-ethoxythiophene), poly(3-butoxythiophene),poly(3-hexyloxythiophene), poly(3-heptyloxythiophene),poly(3-octyloxythiophene), poly(3-decyloxythiophene),poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene),poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene),poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene),poly(3,4-butenedioxythiophene), poly(3-carboxythiophene),poly(3-methyl-4-carboxythiophene),poly(3-methyl-4-carboxyethylthiophene),poly(3-methyl-4-carboxybutylthiophene), polyaniline,poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), poly(3-aniline sulfonate), and the like.

Particularly suitable polymers or co-polymers are selected from thegroup consisting of polypyrrole, polythiophene,poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulphonicacid, salt), poly(N-methylpyrrole), poly(3-methylthiophene),poly(3-methoxythiophene), and poly(3,4-ethylenedioxythiophene).

The polyanion copolymer of Formula A can be used as a counterion topolythiophene comprising repeating units of Formula B. The preferredmolecular weight of polyanion is at least about 100 to no more thanabout 500,000. Below a molecular weight of about 100 film integrity canbe affected and above a molecular weight of about 500,000 conductivityand viscosity can be adversely affected.

The viscosity of each polymer dispersion after polymerization and beforehomogenization is preferably at least 200 cP at 20 RPM to no more than4000 cP at 20 RPM at ambient temperature and preferably at least 600 cPat 20 RPM to no more than 2000 cP at 20 RPM at ambient temperature. Thedispersion has a preferred percent solids of 1 wt % to no more than 5 wt%. More preferably, the polymer dispersion has a percent solids of atleast 2 wt % to no more than 3.5 wt %. The viscosity of the inventivepolymer dispersion after homogenization is preferably less than 100 cPsat 100 RPM, and more preferably less than 50 cPs at 100 RPM.

The dispersion, and polymerization preferably occurs at a temperature ofat least about 15° C. to no more than about 35° C. Below a temperatureof about 15° C. the polymerization rate is very slow and above about 35°C. conductivity and viscosity can be adversely affected.

The first or second conductive polymer dispersions comprising conductivepolymer and polyanion can be further stabilized by polymeric stericstabilizers during or post polymerization. Coagulation or gel formationis significantly reduced due to the insensitivity of the stericallystabilized system to the fluctuations and increases in electrolyteconcentration. In addition, high solids dispersions can be produced bythis method due to the higher stabilizing effect of steric stabilizers.

A criteria for polymeric steric stabilizers for conductive polymerdispersion polymerization is that they must be stable during low pHpolymerization conditions, stable to oxidizing agents, and that they donot interfere with polymerization of the monomer. An exemplary stericstabilizer is a high molecular weight polyethylene oxide and theircopolymers which are preferred as the steric stabilizer due to theirstability in low pH reaction conditions. Another exemplary stericstabilizer is polydimethyl siloxane-polyethylene oxide (PDMS-PEO) blockcopolymer. An advantage of the PDMS-PEO copolymer is that the PDMS blockcould provide moisture resistance in addition to steric stabilization.

Particularly preferred polymeric steric stabilizers comprise linkinggroups which, upon formation of a coated layer, crosslink therebyproviding an interlinked matrix which functions as a binder therebyproviding a coated layer with a suitable structural integrity. Stericstabilizers with a reactive functionality can be employed for postpolymerization crosslinking with the polyanion. Any reactive stericstabilizer with a reactive functionality which is stable during thepolymerization reaction can be used. Examples of such reactivestabilizers are hydroxyl and dihydroxy end capped polybutadiene.Precursors of reactive steric stabilizer can also be employed for postpolymerization activation of the steric stabilizer reactive group.Steric stabilizers are preferably added to the polymerization reactionas solutions in water or other polar solvents such as dimethylsulfoxide, ethylene glycol, N-methyl pyrrolidone, etc.

As used herein, the terminology “steric stabilizer” refers to compoundswhich are adsorbed to the polymer particles of the dispersion andprotective layers around the respective particles to preventagglomeration of the particles.

Suitable steric stabilizers include, for example, protective colloidsand nonionic surfactants having a hydrophilic/lipophilic balance (HLB)greater than about 10. Hydrophilic/lipophilic balance is a measure ofthe degree to which a material is hydrophilic or lipophilic.

Suitable protective colloids include polyethylene oxide, fullyhydrolyzed polyvinyl alcohol, partially hydrolyzed poly(vinyl alcohol),poly(vinyl pyrollidone), hydroxyethyl cellulose, polyethylene oxidecopolymers and their derivatives, and mixtures thereof. Polyethyleneoxide is preferred.

The first or subsequent conductive polymer layers may independentlycomprise substances such as surface-active substances, for example ionicand/or nonionic surfactants; Suitable nonionic surfactants includeethoxylated alkyl phenols, ethoxylated acetylenic diols, polyethyleneoxide-propylene oxide block copolymers as well as mixtures thereof.

The first or second conductive polymer slurry may further comprisecrosslinkers. Cross-linking comprises the use of a material comprisingat least two cross-linkable functionalities wherein one cross-linkablefunctionality forms a first bond and the second cross-linkablefunctionality forms a second bond thereby forming a bridge ofcross-linking molecule between two portions of polymer. Thecross-linkable functionality may form a covalent bond or an ionic bond.The cross-linking provides a process for improved ESR stability byproviding a molecule, oligomer, or polymer with crosslinkablefunctionality in a layer and across layers thereby improving the layerintegrity and the surface coverage. Once exposed to curing conditions,which is typically thermal curing, the crosslinkable molecules reactthus forming a strongly bound interpenetrating network of covalent andionic bonds. The reaction of the crosslinkable functionality and thecrosslinker occurs at elevated temperature which occurs during thenormal processing steps of capacitor manufacture.

The crosslinkable materials preferably comprise two components with onecomponent preferably being a compound, oligomer or polymer withmultifunctional or multiple reactive groups. The second component ispreferably a molecule with crosslinkable functionality preferablyselected from the group consisting of carboxylic, hydroxyl, amine,epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylicanhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates,maleimides, itaconates, allyl alcohol esters, dicyclo-pentadiene-basedunsaturations, unsaturated C₁₂-C₂₂ fatty esters or amides, carboxylicacid salts or quaternary ammonium salts.

One embodiment includes a solid electrolytic capacitor comprising acrosslinkable material system wherein an oligomer or polymer comprisesmultifunctional reactive groups selected from the group consisting ofpolyester, polyurethane, polyamide, polyamine, polyimide, siliconepolyester, hydroxyl functional silicone, hydroxyethyl cellulose,polyvinyl alcohol, phenolic, epoxy, butyral, copolymers of these ormixture of these multifunctional polymers such as epoxy/amine,epoxy/anhydride, isocyanate/amine, isocyanate/alcohol, unsaturatedpolyesters, vinyl esters, unsaturated polyester and vinyl ester blends,unsaturated polyester/urethane hybrid resins, polyurethane-ureas,reactive dicyclopentadiene resins or reactive polyamides. The oligomeror polymer with multifunctional or multiple reactive groups preferablyincludes at least one carboxylic acid group and at least one hydroxylfunction group. A particularly preferred oligomer or polymer withmultifunctional reactive groups is a polyester containing carboxylic andhydroxyl functionality. In addition to oligomers or polymers, particleswith surface functional groups can also take part in the crosslinking.Particles with functional groups are preferred wherein the functionalgroups are selected from carboxylic, hydroxyl, amine, epoxy, anhydride,isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane,oxazoline, (meth)acrylates, vinyls, maleates, maleimides, itaconates,allyl alcohol esters, dicyclo-pentadiene-based unsaturations,unsaturated C₁₂-C₂₂ fatty esters or amides, carboxylic acid salts orquaternary ammonium salts. Particles can be nanoparticles ormicroparticles. One example of functionalized nanoparticles isorganomodified nanoclay.

In an embodiment at least one conductive layer further comprises organicor inorganic particles or fibers with reactive functional groups orcarbon particle filled polymer, a metal particle filled polymer and aconductive particle filled polymer or particles of fibers with reactivefunctional groups or crosslinkable groups.

The first or subsequent conductive polymer layers may independentlycomprise additives which enhance the conductivity, for example compoundscontaining ether groups, for example tetrahydrofuran; compoundscontaining lactone groups, such as y-butyrolactone, r-valerolactone;compounds containing amide or lactam groups, such as caprolactam,N-methylcaprolactam, N,N-dimethylacetamide, N-methyl-acetamide,N,N-dimethylformamide (DMF), N-methyl-formamide, N-methylformanilide,N-methylpyrrolidone (NMP), N-octylpyrrolidone, pyrrolidone; sulfones andsulfoxides, for example sulfolane(tetramethylenesulfone), dimethylsulfoxide (DMSO); sugars or sugar derivatives, for example sucrose,glucose, fructose, lactose, sugar alcohols, for example sorbitol,mannitol; imides, for example succinimide or maleimide; furanderivatives, for example 2-furancarboxylic acid, 3-furancarboxylic acid,and/or di-or polyalcohols, for example ethylene glycol, glycerol ordi-or triethylene glycol. Preference is given to using, asconductivity-enhancing additives, ethylene glycol, dimethyl sulfoxide,glycerol or sorbitol.

The first or second slurry preferably comprises reactive monomers, whichmay function as film formers, can improve polymer film strength upondrying of the film. The reactive monomer or oligomers can be soluble inwater or organic solvent or disperse in water through the use ofionic/non-ionic surfactant. The reactive monomers can have averagefunctionalities of at least two and preferably more. The curing processof the monomer can be catalyzed by using heat, radiation or chemicalcatalysis. Examples of monomers such as compounds having more than oneepoxy group includes ethylene glycol diglycidyl ether (EGDGE), propyleneglycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether(BDDGE), pentylene glycol diglycidyl ether, hexylene glycol diglycidylether, cyclohexane dimethanol diglycidyl ether, resorcinol glycidylether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ethers,diglycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers,sorbitol diglycidyl ether (Sorbitol-DGE), sorbitol polyglycidyl ethers,polyethylene glycol diglycidyl ether (PEGDGE), polypropylene glycoldiglycidyl ether, polytetramethylene glycol diglycidyl ether,di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadienediepoxide, 1,2,7,8-diepoxyociane, 1,2,5,6-diepoxycycloociane, 4-vinylcyclohexane diepoxide, bisphenol A diglycidyl ether, maleimide-epoxycompounds, diglycidyl ether, glycidyl acrylate, glycidyl methacrylate,waterborne dispersion of epoxy resins such as bisphenol A epoxy resin,epoxidized Bisphenol A novolac modified epoxy resin, urethane modifiedBisphenol A epoxy resin, an epoxidized o-cresylic novolac resin and soforth.

Examples of other suitable monomers containing acidic groups, i.e.oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioicacid, phthalic acids, maleic acid, muconic acid, citric acid, irimesicacid, polyacrylic acid, etc. Particularly preferred organic acids arearomatic acid such as phthalic acid, and particularly ortho-phthalicacid.

Examples of suitable monomers containing alcohol/acrylate groups, suchas, diethylene glycol, pentaerythritol, triethylene glycol,oligo/polyethylene glycol, triethylene glycol monochlorohydrin,diethylene glycol monochlorohydrin, oligo ethylene glycolmonochlorohydrin, triethylene glycol monobromohydrin, diethylene glycolmonobromohydrin, oligo ethylene glycol monobromohydrin, polyethyleneglycol, polyether, polyethylene oxide, triethylene glycol-dimethylether,tetraethylene glycol-dimethylether, diethylene glycol-dimethylether,diethylene glycol-diethylether-diethylene glycol-dibutylether,dipropylene glycol, tripropylene glycol, polypropylene glycol,polypropylene dioxide, polyoxyethylene alkylether, polyoxyethyleneglycerin fatty acid ester, polyoxyethylene fatly acid amide,2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butoxyethylmethacrylate, n-butoxyethylene glycol methacrylate, methoxytriethyleneglycol methacrylate, methoxypolyethylene glycol methacrylate,2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, n-butoxyethylacrylate, n-butoxyethylene glycol acrylate, methoxytriethylene glycolacrylate, ethoxypolyethylene glycol acrylate, and the like; bifunctional(meth)acrylate compounds, such as, ethylene glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,glycerin di(meth)acrylate, and the like; glycidyl ethers, such as,ethylene glycol diglycidyl ether, glycidyl ether, diethylene glycoldiglycidyl ether, triethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, propylene glycidyl ether, tripropylene glycidylether, polypropylene glycidyl ether, glycerin diglycidyl ether, and thelike; glycidyl methacrylate, trimethylolpropane triacrylate, ethyleneoxide-modified trimethylolpropane triacrylate, ethylene oxide-modifiedpentaerythritol triacrylate, ethylene oxide-modified pentaerythritoltetraacrylate, and the like.

The first or subsequent conductive polymer layers may also independentlycomprise polyanions containing reactive groups such as epoxy, alcohol,silanes, phosphates, amine, alkene, thiol, alkyne, azide carboxylicacid.

The first or subsequent conductive polymer layers may also independentlycomprise linear hyperbranched polymers disclosed in patent U.S. Pat. No.9,378,898. The first or subsequent conductive polymer layers maycomprise a linear-hyperbranched polymer where the linear block has atleast two reactive end functional groups selected from hydroxyl groups,amino groups, epoxy, acrylate, acid etc. and where the hyper-branchedblock comprises polyether-epoxy, polyester-epoxy, polyester-silanol,polyester-acid, polyether-alcohol, polyamide-acid, polyether-acrylate,polyether-silanol and polyester-amine pendant groups.

The first or subsequent conductive polymer layers may furtherindependently comprise work function modifiers disclosed in U.S. Publ.No. 20150348715 A1. Examples of work function modifiers such asorganotitanates derivatives selected from the group consisting ofdi-alkoxy acyl titanate, tri-alkoxy acyl titanate, alkoxy triacyltitantate, alkoxy titantate, neoalkoxy titanate, titanium IV 2,2(bis2-propenolatomethyl)butanolato, tris neodecanoato-O; titanium IV 2,2(bis2-propenolatomethyl)butanolato, iris(dodecyl)benzenesulfonato-O;titanium IV 2,2(bis 2-propenolatomethyl)butanolato,tris(dioctyl)phosphato-O; titanium IV 2,2(bis 2-propenolatomethyl)tris(dioctyl)pyrophosphatobutanolato-O; titanium IV 2,2(bis2-propenolatomethyl) butanolato, tris(2-ethylenediamino)ethylato; andtitanium IV 2,2(bis 2-propenolatomethyl)butanolato,tris(3-amino)phenylato being representative neoalkoxy titanates andderivatives thereof. Furthermore, work function modifier can be acompounds consisting of cycloaliphatic epoxy resin, ethylene glycoldiglycidyl ether, bisphenol A epoxy resin, bisphenol F epoxy resin,bisphenol S epoxy resin, novolac epoxy resin, aliphatic epoxy resin,Glycidylamine epoxy resin, ethylene glycol diglycidyl ether (EGDGE),propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidylether (BDDGE), pentylene glycol diglycidyl ether, hexylene glycoldiglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinolglycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidylethers, diglycerol polyglycidyl ethers, trimethylolpropane polyglycidylethers, sorbitol diglycidyl ether (Sorbitol-DGE), sorbitol polyglycidylethers, polyethylene glycol diglycidyl ether (PEGDGE), polypropyleneglycol diglycidyl ether, polytetramethylene glycol diglycidyl ether,di(2,3-epoxypropyl)ether, 1,3-butadiene diepoxide, 1,5-hexadienediepoxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxycompounds, and derivatives thereof.

The first or subsequent conductive polymer layers may furtherindependently comprise nonionic polymer such as a hydroxy-functionalnonionic polymer. The term “hydroxy-functional” generally means that thecompound contains at least one hydroxyl functional group. The molecularweight of the hydroxy-functional polymer may be from about 100 to 10,000grams per mole, in some embodiments from about 200 to 2,000, in someembodiments from about 300 to about 1,200, and in some embodiments, fromabout 400 to about 800.

Any of a variety of hydroxy-functional nonionic polymers may generallybe employed. In one embodiment, for example, the hydroxy-functionalpolymer is a polyalkylene ether. Polyalkylene ethers may includepolyalkylene glycols (e.g., polyethylene glycols, polypropylene glycolspolytetramethylene glycols, polyepichlorohydrins, etc.), polyoxetanes,polyphenylene ethers, polyether ketones, and so forth. Polyalkyleneethers are typically predominantly linear, nonionic polymers withterminal hydroxy groups. Particularly suitable are polyethylene glycols,polypropylene glycols and polytetramethylene glycols(polytetrahydrofurans). The diol component may be selected, inparticular, from saturated or unsaturated, branched or unbranched,aliphatic dihydroxy compounds containing 5 to 36 carbon atoms oraromatic dihydroxy compounds, such as, for example, pentane-1,5-diol,hexane-1,6-diol, neopentyl glycol, bis-(hydroxymethyl)-cyclohexanes,bisphenol A, dimer diols, hydrogenated dimer diols or even mixtures ofthe diols mentioned.

In addition to those noted above, other hydroxy-functional nonionicpolymers may also be employed. Some examples of such polymers include,for instance, ethoxylated alkylphenols; ethoxylated or propoxylatedC₆-C₂₄ fatty alcohols; polyoxyethylene glycol alkyl ethers having thegeneral formula: CH₃—(CH₂)₁₀₋₁₆—(O—C₂H₄)₁₋₂₅—OH (e.g., octaethyleneglycol monododecyl ether and pentaethylene glycol monododecyl ether);polyoxypropylene glycol alkyl ethers having the general formula:CH₃—(CH₂)₁₀₋₁₆—(O—C₃H₆)₁₋₂₅—OH; polyoxyethylene glycol octylphenolethers having the following general formula:C₈—H₁₇—(C₆H₄)—(O—C₂H₄)₁₋₂₅—OH (e.g., Triton™ X-100); polyoxyethyleneglycol alkylphenol ethers having the following general formula:C₉—H₁₉—(C₆H₄)—(O—C₂H₄)₁₋₂₅—OH (e.g., nonoxynol-9); polyoxyethyleneglycol esters of C₈-C₂₄ fatty acids, such as polyoxyethylene glycolsorbitan alkyl esters (e.g., polyoxyethylene (20) sorbitan monolaurate,polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20)sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, PEG-20methyl glucose distearate, PEG-20 methyl glucose sesquistearate, PEG-80castor oil, and PEG-20 castor oil, PEG-3 castor oil, PEG 600 dioleate,and PEG 400 dioleate) and polyoxyethylene glycerol alkyl esters (e.g.,polyoxyethylene-23 glycerol laurate and polyoxyethylene-20 glycerolstearate); polyoxyethylene glycol ethers of C₈-C₂₄ fatty acids (e.g.,polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether,polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether,polyoxyethylene-20 oleyl ether, polyoxyethylene-20 isohexadecyl ether,polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecylether); block copolymers of polyethylene glycol and so forth.

The first or second slurry can comprise ionic liquids includingpoly(ionic liquids) (PILs). Ionic liquids can also be applied as aseparate layer before or after the conductive polymer dispersion. Ionicliquids (ILs) are generally defined as organic/inorganic salts with amelting point lower than 100° C. which present a good chemical andelectrochemical stability, low flammability, negligible vapor pressureand high ionic conductivity. In a liquid state and with negligible vaporpressure, ionic liquids are commonly considered as green solvents forindustrial production. Ionic liquids are organic salts in which the ionsare poorly coordinated and melt below 100° C., or even at roomtemperature. Ionic liquids have a wide electrochemical operationalwindow and comparably high matrix mobility at room temperature. Becauseionic liquids are entirely composed of ions, their charge density ismuch higher than that of an ordinary salt solution. For applications incapacitors, due to the unique charged structure of the ionic liquids,they may form complex with conductive polymers that also have chargedcations and anions and this may affect the impregnation behavior of theconductive polymer particles. Ionic liquids could also affect healing ofdielectric under electrical field and therefore benefit leakage andbreakdown voltage of capacitors. Ionic liquids are composed of thecationic component and the anionic component. Examples of cationiccomponent include: ammonium, imidazolinium, pyridinium, pyrrolidinium,pyrrolinium, pyrazinium, pyrimidinium, triazonium, triazinium, triazine,quinolinium, isoquinolinium, indolinium, quinoxalinium, piperazinium,oxazolinium, thiazolinium, morpholinium, piperazine, sulfonium and theirderivatives. The cations can be substituted with functional groups suchas aliphatic, alicyclic or aromatic hydrocarbons, hydroxy, amino,carboxylic acids, ester, ether, acyl, and acryl functional groups. thecation component is preferably an ammonium or imidazolium. Examples ofthe anionic component include fluorine-containing anions such as BF₄ ⁻,PF₆ ⁻, CF₃BF₃ ⁻, C₂F₅BF₃ ⁻, CH₂CHBF₃ ⁻, nC₃H₇BF₃ ⁻, nC₄H₉BF₃ ⁻, CF₃CO₂⁻, CF₃SO₃ ⁻, CHF₂CF₂CF₂CF₂CH₂OSO₃ ⁻, CHF₂CF₂CF₂CF₂CH₂SO₃ ⁻, (CF₃SO₂)₂N⁻,(CF₃SO₂)₃C⁻, (COCF₃)(SO₂CF₃)N⁻, and non-fluorine-containing anions suchas B(CN)₄ ⁻, N(CN)₂ ⁻, C(CN)₃ ⁻, SCN⁻, SeCN⁻, AlCl4⁻, OH⁻, CH₃SO₃ ⁻,CH₃OSO₃ ⁻, (CH₃CH₂)PO₄ ⁻, and their derivatives.

Poly(ionic liquids)s (PILs), refer to a subclass of polyelectrolytesthat feature an ionic liquid species in each monomer repeating unit,connected through a polymeric backbone to form a macromoleculararchitecture as set forth in Progress in Polymer Science Volume 38,Issue 7, July 2013, Pages 1009-1036. Some of the unique properties ofionic liquids are incorporated into the polymer chains, giving rise to anew class of polymeric materials. Polymeric ionic liquids expand theproperties and applications of ionic liquids and commonpolyelectrolytes. Due to the solvent-independent ionization state of theionic liquid species, polymeric ionic liquids are permanent and strongpolyelectrolytes. The characteristic feature of absorbing water is acommon feature of ionic liquids and polymeric ionic liquids.

Exemplary polymeric ionic liquids are selected from the group consistingof:

1-ethyl-3-methylimidazolium tetrafluoroborate and derivatives thereof.

The first or second slurry may have a pH of 1 to 14, preference beinggiven to a pH of 1 to 10, particularly preferred is a pH of 1 to 8 withthe pH being measured at 25° C. To adjust the pH, bases or acids, forexample, can be added to the solutions or dispersions. The bases usedmay be inorganic bases, for example sodium hydroxide, potassiumhydroxide, calcium hydroxide or ammonia, or organic bases, for exampleethylarnine, diethylamine, triethylamine, propylamine, dipropylamine,tripropylamine, isopropylamine, diisopropylamine, butylamine,dibutylamine, tributylamine, isobutylamine, diisobutylamine,triisobutylamine, 1-methylpropylamine, methylethylamine,bis(1-methyl)propylamine, 1,1-di-methylethylamine, pentylamine,dipentylamine, tiripentylamine, 2-pentylamine, 3-pentylamine,2-methyl-butylamine, 3-methylbutylamine, bis(3-methyl-butylamine),tris(3-methylbutylamine), hexylamine, octylamine, 2-ethylhexylamine,decylamine, N-methyl-butylamine, N-ethylbutylamine,N,N-dimethylethylamine, N,N-dimethylpropyl, N-ethyldiisopropylamine,allylamine, diallylamine, ethanolamine, diethanolarnine,triethanolamine, methylethanolamine, methyl-diethanolamine,dimethylethanolamine, diethyl-ethanolamine, N-butylethanolamine,N-butyldiethanol-amine, dibutylethanolamine, cyclohexylethanolamine,cyclohexyldiethanolamine, N-ethylethanolamine, N-propylethanolamine,tert-butylethanolamine, tert-butyl-diethanolarnine, propanolamine,dipropanolamine, tripropanolamine or benzylamine, bi-, tri-, ortetra-functional amines. The acids used may be inorganic acids, forexample sulfuric acid, phosphoric acid or nitric acid, or organic acids,for example carboxylic or sulfonic acids.

The anode material is not limited herein. The anode is a conductorpreferably selected from a metal or a conductive metal oxide. Aparticularly preferred anode material is a metal and a particularlypreferred metal is a valve metal or a conductive oxide of a valve metal.More preferably the anode comprises a mixture, alloy or conductive oxideof a valve metal preferably selected from Al, W, Ta, Nb, Ti, Zr and Hf.Particularly preferred anodes include niobium, aluminum, tantalum andNbO without limit thereto. An anode consisting essentially of Ta is mostpreferred.

The dielectric is a non-conductive layer which is not particularlylimited herein. The dielectric may be a metal oxide or a ceramicmaterial. A particularly preferred dielectric is a non-conductive oxideof a metal anode due to the simplicity of formation and ease of use. Thedielectric is preferably formed by dipping the anode into an anodizingsolution with electrochemical conversion. Alternatively, a dielectricprecursor can be applied by spraying or printing followed by sinteringto form the layer. When the dielectric is an oxide of the anode materialdipping is a preferred method whereas when the dielectric is a differentmaterial, such as a ceramic, a spraying or coating technique ispreferred.

The anode lead wire is chosen to have low resistivity and to becompatible with the anode material. The anode lead wire may have thesame composition as the anode material or may be a conductive oxidethereof. Particularly preferred anode lead wires include Ta, Nb and NbO.The shape of the anode lead wire is not particularly limiting. Preferredshapes include round, oval, rectangular and combinations thereof. Theshape of the anode lead wire is chosen for optimum electrical propertiesof the ultimate capacitor.

Throughout the description the terms slurry and dispersion are usedinterchangeably.

Throughout the description terms such as “alkyl”, “aryl”, “alkylaryl”,“arylalkyl” refer to unsubstituted or substituted groups and if alreadylisted as substituted, such as “alkyl alcohol” refer to groups which arenot further substituted or may be further substituted.

Tests

Capacitance Recovery % is the capacitance ratio in percentage ofencapsulated parts to capacitance of these parts tested in a liquidelectrolyte before cathode layers are applied. ESR is equivalent seriesresistance of encapsulated capacitors. DCL is leakage current ofencapsulated capacitors. BDV is the Breakdown Voltage of theencapsulated capacitors. Vf is the formation voltage applied to anode toform the dielectric layer. Power Cycling Test was done at ambient roomtemperature, with rated voltage on for 5 seconds, followed by turningoff the voltage for 5 seconds. The voltage on/off cycle was repeated for60,000 times. Capacitance of the parts were tested before and after thepower cycling cycles and the % capacitance change is calculated.

EXAMPLES Prep. Example 1

A dispersion comprising PSSA and PEDOT in a weight ratio of 2 wasprepared. A 4 L plastic jar with a cooling jacket was initially chargedwith 71.76 g of Polystyrene Sulfonic Acid (PSSA) 30% solution in water,1669 g of deionized (DI) water, 27.27 g of 1% iron(III) sulphate, and20.57 g of sodium peroxodisulphate. The contents were mixed using arotor-stator mixing system with perforated stator screen with a roundhole size diameter of 1.6 mm. Subsequently, 10.76 g of3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reactionmixture was sheared continuously with a shear speed of 4200 RPM with therotor-stator mixing system for an additional 23 hours. The dispersionwas treated with cationic and anionic exchange resin and filtered to getPEDOT-PSSA base slurry. The PEDOT-PSSA base slurry was furtherhomogenized with an ultrasonicator. Conductivity of the dispersion was259 S/cm, as tested with DMSO additive, and D50 was 18.1 nm.

Prep. Example 2

A PSSA/PEDOT slurry was prepared in a weight ratio of 3.3. A 4 L plasticjar provided with a cooling jacket was initially charged with 125 g ofPolystyrene Sulfonic Acid (PSSA) 30% solution in water, 2531 g of DIwater, 28.5 g of 1% iron(III) sulphate, and 21.5 g of sodiumperoxodisulphate. The contents were mixed using a rotor-stator mixingsystem with perforated stator screen with a round hole size diameter of1.6 mm. Subsequently, 11.25 g of 3,4-ethylenedioxythiophene (EDOT) wasadded dropwise. The reaction mixture was sheared continuously with ashear speed of 8000 RPM with the rotor-stator mixing system for anadditional 23 hours. The dispersion was treated with cationic andanionic exchange resin and filtered to get PEDOT-PSSA base slurry. ThePEDOT-PSSA base slurry was further homogenized with an ultrasonicator.Conductivity of the dispersion was 210 S/cm, as tested with DMSOadditive, and D50 was 15.0 nm.

Prep. Example 3

A PSSA/PEDOT slurry was prepared in a weight ratio of 3.3. A 4 L plasticjar, provided with a cooling jacket, was initially charged with 92.00 gof Polystyrene Sulfonic Acid (PSSA) 30% solution in water (sonicated for2 hrs before mixing), 1863 g of DI water, 20.98 g of 1% iron(III)sulphate, and 15.82 g of sodium peroxodisulphate. The contents weremixed using a rotor-stator mixing system with perforated stator screenwith a round hole size diameter of 1.6 mm. Subsequently, 8.28 g of3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reactionmixture was sheared continuously with a shear speed of 4200 RPM with therotor-stator mixing system for an additional 23 hours. The dispersionwas treated with cationic and anionic exchange resin and filtered to getPEDOT-PSSA base slurry. The PEDOT-PSSA base slurry was furtherhomogenized with an ultrasonicator. Conductivity of the dispersion was257 S/cm, as tested with DMSO additive, and D50 was 13.8 nm.

Prep. Example 4

A PSSA/PEDOT slurry was prepared in a weight ratio of 5.0. A 4 L plasticjar, provided with a cooling jacket, was initially charged with 54.82 gof Polystyrene Sulfonic Acid (PSSA) 30% solution in water, 1028 g of DIwater, 6.80 g of 1% iron(III) sulphate, and 6.29 g of sodiumperoxodisulphate. The contents were mixed using a rotor-stator mixingsystem with perforated stator screen with a round hole size diameter of1.6 mm. Subsequently, 3.29 g of 3,4-ethylenedioxythiophene (EDOT) wasadded dropwise. The reaction mixture was sheared continuously with ashear speed of 5000 RPM with the rotor-stator mixing system for anadditional 23 hours. The dispersion was treated with cationic andanionic exchange resin and filtered to get PEDOT-PSSA base slurry. ThePEDOT-PSSA base slurry was further homogenized with an ultrasonicator.Conductivity of the dispersion was 162 S/cm, as tested with DMSOadditive, and D50 was 14.7 nm.

Prep. Example 5

A ST/PEDOT slurry was prepared in a weight ratio of 1.5. A 4 L plasticjar provided with a cooling jacket was initially charged with 55.81 g ofa polystyrene-sodium polystyrene sulfonate copolymer (ST) 20% solutionin water, 1290 g of DI water, 2.98 g of concentrated sulfuric acid,31.54 g of 1% iron(III) sulphate, and 14.58 g of sodiumperoxodisulphate. The contents were mixed using a rotor-stator mixingsystem with perforated stator screen with a round hole size diameter of1.6 mm. Subsequently, 7.63 g of 3,4-ethylenedioxythiophene (EDOT) wasadded dropwise. The reaction mixture was sheared continuously with ashear speed of 6000 RPM with the rotor-stator mixing system for anadditional 23 hours. The dispersion was treated with cationic andanionic exchange resin and filtered to get PEDOT-PSSA base slurry. ThePEDOT-PSSA base slurry was further homogenized with an ultrasonicator.Conductivity of the dispersion was 151 S/cm, as tested with DMSOadditive, and D50 was 16.1 nm.

Prep. Example 6

A ST/PEDOT slurry was prepared in a weight ratio of 2.6. A 4 L plasticjar, provided with a cooling jacket, was initially charged with 87.86 gof a polystyrene-sodium polystyrene sulfonate (ST) copolymer 20%solution in water, 1644 g of DI water, 4.70 g of concentrated sulfuricacid, 28.59 g of 1% iron(III) sulphate, and 13.22 g of sodiumperoxodisulphate. The contents were mixed using a rotor-stator mixingsystem with perforated stator screen with a round hole size diameter of1.6 mm. Subsequently, 6.92 g of 3,4-ethylenedioxythiophene (EDOT) wasadded dropwise. The reaction mixture was sheared continuously with ashear speed of 6000 RPM with the rotor-stator mixing system for anadditional 23 hours. The dispersion was treated with cationic andanionic exchange resin and filtered to get PEDOT-PSSA base slurry. ThePEDOT-PSSA base slurry was further homogenized with an ultrasonicator.Conductivity of the dispersion was 125 S/cm, as tested with DMSOadditive, and D50 was 13.3 nm.

Prep. Example 7

A ST/PEDOT slurry was prepared in a weight ratio of 3.5. A 4 L plasticjar, provided with a cooling jacket, was initially charged with 58.31 gof a polystyrene-sodium polystyrene sulfonate copolymer (ST) 20%solution in water, 1025 g of DI water, 3.12 g of concentrated sulfuricacid, 7.12 g of 1% iron(III) sulphate, and 6.59 g of sodiumperoxodisulphate. The contents were mixed using a rotor-stator mixingsystem with perforated stator screen with a round hole size diameter of1.6 mm. Subsequently, 6.92 g of 3,4-ethylenedioxythiophene (EDOT) wasadded dropwise. The reaction mixture was sheared continuously with ashear speed of 6000 RPM with the rotor-stator mixing system for anadditional 23 hours. The dispersion was treated with cationic andanionic exchange resin and filtered to get PEDOT-PSSA base slurry. ThePEDOT-PSSA base slurry was further homogenized with an ultrasonicator.Conductivity of the dispersion was 94 S/cm, as tested with DMSOadditive, and D50 was 12.9 nm.

Prep. Example 8

Soluble conductive polymer (S1) was prepared. Commercially availablehydroxymethyl 3,4-ethylenedioxythiophene (0.50 g) dissolved intetrahydrofuran was added to sodium hydride (0.084 g) under nitrogenatmosphere. The resulting mixture was refluxed for one hour, after which1,4-butanesultone (0.41 g) dissolved in tetrahydrofuran (8 ml) wasslowly added. The mixture was stirred for two more hours and thenallowed to cool. Acetone (45 ml) was poured into the mixture undervigorous stirring. The suspension was filtered, washed with hot acetone,and concentrated under vacuum to yield pale orange powder of monomer.

0.2 g monomer dissolved in water (5 ml) was added to 0.9 gm iron (III)p-toluenesulfonate hexahydate. The resulting mixture was polymerizedunder nitrogen for 24 hours at room temperature. The resulting S1polymer was isolated by precipitating in acetone. The precipitate wascollected through vacuum filtration. The collected precipitate wasdissolved in DI water and treated with ion exchange resin for 6 hours.The resulting dark blue solution of conductive polymer S1 was isolatedthrough vacuum filtration. The measured electrical conductivity of S1was 5 S/cm.

Prep. Example 9

To 81 g of Prep. Example 4 was added 9 g of a soluble conductive polymeraqueous solution (S2)

Prep. Example 10

To 100 g of Clevios Knano LV was added 0.4 g of3-glycidoxypropyltrimethoxysilane and 1.2 g of a polyethyleneglycoldiglycidyl ether. The measured D50 was 16.4 nm.

Inventive Example 1 (I-1)

A series of 47 microfarads, 16V tantalum anodes with a specific chargeof 133,000 μFV/g were prepared. The tantalum was anodized to form adielectric on the tantalum anode. The anode thus formed was dipped intoPrep. Example 2 for 1 minute and oven dried to remove water. Thisprocess was repeated until a sufficient thickness was achieved. A secondconductive polymer dispersion containing epoxy and silane compounds wasapplied to form a subsequent polymer layer. After drying, alternatinglayers of a diamine salt and the second conductive polymer dispersionwas applied and repeated 4-5 more times. The anodes with the conductivepolymer layers were washed and dried, followed by sequential coating ofa graphite layer and a silver layer to produce a solid electrolyticcapacitor. Parts were assembled and packaged. Capacitance and ESR weremeasured on packaged parts.

Inventive Example 2 (I-2)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 4.

Comp. Example 1 (C-1)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasa commercial Clevios Knano LV sample from Heraeus. Knano LV was reportedto have polyanion/EDOT weight ratio of 2.5.

Comp. Example 2 (C-2)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 1.

Comp. Example 3 (C-3)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 3.

Inventive Example 3 (I-3)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 7.

Comp. Example 4 (C-4)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 5.

Comp. Example 5 (C-5)

A series of Tantalum capacitors were prepared as described in InventiveExample 1, except that the first conductive polymer dispersion used wasPrep. Example 6.

Inventive Example 4 (I-4)

A series of tantalum anodes (33 microfarads, 16V, with a specific chargeof 65,000 μFV/g) were prepared. The tantalum was anodized to form adielectric on the tantalum anode. The anode thus formed was dipped intoPrep. Example 4 for 1 minute and oven dried to remove water. Thisprocess was repeated until a sufficient thickness was achieved. A secondconductive polymer dispersion containing epoxy and silane compounds wasapplied to form a subsequent polymer layer. After drying, alternatinglayers of a diamine salt and the second conductive polymer dispersionwas applied and repeated 4-5 more times. The anodes with the conductivepolymer layers were washed and dried, followed by sequential coating ofa graphite layer and a silver layer to produce a solid electrolyticcapacitor. Parts were assembled and packaged. Capacitance and ESR wasmeasured on packaged parts.

Comp. Example 6 (C-6)

A series of Tantalum capacitors were prepared as described in InventiveExample 4, except that the first conductive polymer dispersion used wasa commercial Clevios Knano LV sample from Heraeus.

Inventive Example 5 (I-5)

A series of 68 microfarads, 16V tantalum anodes with a specific chargeof 48,000 μFV/g were prepared. The tantalum was anodized to form adielectric on the tantalum anode. The anode thus formed was dipped intoPrep. Example 2 for 1 minute and oven dried to remove water. Thisprocess was repeated until a sufficient thickness was achieved. A secondconductive polymer dispersion containing epoxy and silane compounds wasapplied to form an external polymer layer. After drying, alternatinglayers of a diamine salt and the second conductive polymer dispersionwas applied and repeated 4-5 more times. The anodes with the conductivepolymer layers were washed and dried, followed by sequential coating ofa graphite layer and a silver layer to produce a solid electrolyticcapacitor. Parts were assembled and packaged. Capacitance and ESR weremeasured on packaged parts.

Inventive Example 6 (I-6)

A series of Tantalum capacitors were prepared as described in InventiveExample 5, except that the first conductive polymer dispersion used wasPrep. Example 4.

Comp. Example 7 (C-7)

A series of Tantalum capacitors were prepared as described in InventiveExample 5, except that the first conductive polymer dispersion used wasa commercial Clevios Knano LV sample from Heraeus.

Inventive Example 7 (I-7)

A series of tantalum anodes (4.7 microfarads, 63V, with a specificcharge of 13,000 μFV/g) were prepared. The tantalum was anodized to forma dielectric on the tantalum anode. The anode thus formed was dippedinto Prep. Example 4 for 1 minute and oven dried to remove water. Thisprocess was repeated until a sufficient thickness was achieved. A secondconductive polymer dispersion containing epoxy and silane compounds wasapplied to form a subsequent polymer layer. After drying, alternatinglayers of a diamine salt and the second conductive polymer dispersionwas applied and repeated 4-5 more times. The anodes with the conductivepolymer layers were washed and dried, followed by sequential coating ofa graphite layer and a silver layer to produce a solid electrolyticcapacitor. Parts were assembled and packaged. Capacitance and ESR weremeasured on packaged parts.

Comparative Example 8 (C-8)

A series of Tantalum capacitors were prepared as described in InventiveExample 7, except that the first conductive polymer dispersion used wasa commercial Clevios Knano LV sample from Heraeus.

Inventive Example 8 (I-8)

A series of 47 microfarads, 16 V tantalum anodes with a specific chargeof 133,000 μFV/g were prepared. The tantalum was anodized to form adielectric on the tantalum anode. The anode thus formed was dipped intoS1, Prep. Example 8, for 1 min and oven dried to remove water. Thisprocess was repeated one more time. The anode was then dipped in Prep.Example 2 for 1 minute and oven dried to remove water. This process wasrepeated until a sufficient thickness was achieved. A commercialconductive polymer dispersion KV2 from Heraeus was then applied to forma subsequent polymer layer. After drying, alternating layers of adiamine salt solution and the commercial conductive polymer dispersionwas applied and repeated 4-5 more times. The anodes with the conductivepolymer layers were washed and dried, followed by sequential coating ofa graphite layer and a silver layer to produce a solid electrolyticcapacitor. Parts were assembled and packaged. Capacitance and ESR weremeasured on packaged parts.

Inventive Example 9 (I-9)

A series of Tantalum capacitors were prepared as described in InventiveExample 8, except that Prep. Example 2 was replaced by Prep. Example 4.

Comparative Example 9 (C-9)

A series of Tantalum capacitors were prepared as described in InventiveExample 8, except that Prep. Example 2 was replaced by a commercialClevios Knano LV sample from Heraeus.

Comparative Example 10 (C-10)

A series of Tantalum capacitors were prepared as described in InventiveExample 8, except that Prep. Example 2 was replaced by soluble PEDOTsolution S1 from Prep. Example 8.

Inventive Example 10 (I-10)

A series of 47 microfarads, 16V tantalum anodes with a specific chargeof 133,000 μFV/g were prepared as described in Inventive Example 1,except that Prep. Example 2 was replaced by Prep. Example 9.

Comparative Example 11 (C-11)

A series of 47 microfarads, 16V tantalum anodes with a specific chargeof 133,000 μFV/g were prepared as described in Inventive Example 1,except that Prep. Example 2 was replaced by a soluble conductive polymeraqueous solution (S2).

Inv. Example 11 (I-11)

A series of 33 microfarads, 35V tantalum anodes with a specific chargeof 22,000 μFV/g were prepared. The tantalum was anodized to form adielectric on the tantalum anode. The anodized anode thus formed wasdipped into a solution of iron (III) toluenesulfonate oxidant for 1minute and sequentially dipped into ethyldioxythiophene monomer for 1minute. The anodes were washed to remove excess monomer and by-productsof the reactions after the completion of 60 minutes polymerization,which formed a thin layer of conductive polymer (PEDOT) on thedielectric of the anodized anodes. The anode was dipped into acommercial conductive polymer dispersion Clevios Knano LV from Heraeusfor 1 min and oven dried to remove water. This process was repeatedthree more times. The same dipping and drying process was repeated threetimes with a conductive polymer dispersion from Prep. Example 10. Acommercial conductive polymer dispersion KV2 from Heraeus was thenapplied to form an external polymer layer. After drying, alternatinglayers of a diamine salt solution and the commercial conductive polymerdispersion was applied and repeated 4-5 more times. The anodes with theconductive polymer layers were washed and dried, followed by sequentialcoating of a graphite layer and a silver layer to produce a solidelectrolytic capacitor. Parts were assembled and packaged. Capacitance,ESR, leakage and BDV were measured on packaged parts.

Comp. Example 12 (C-12)

A series of Tantalum capacitors were prepared as described in InventiveExample 13, except that all 7 cycles of first conductive polymerdispersion used a commercial conductive polymer dispersion Clevios KnanoLV.

TABLE 1 Powder D50 Charge Capicitance ESR Samples Polyanion Ratio (nm)(μFV/g) Recovery % (mΩ) I-1 PSSA 3.3 15 133,000 15.5 146.0 I-2 PSSA 514.7 133,000 49.9 119.1 C-1 PSSA 2.5 15.5 133,000 5.9 151.5 C-2 PSSA 218.1 133,000 3.7 251.3 C-3 PSSA 3.3 13.8 133,000 16.1 169.5 I-3 ST 3.512.9 133,000 52.1 145.9 C-4 ST 1.5 16.1 133,000 3.5 305.1 C-5 ST 2.613.3 133,000 20.7 193.7 I-7 PSSA 5 14.7 13,000 77.9 53.7 C-8 PSSA 2.515.5 13,000 76.8 50.5

In Table 1 Ratio is the weight ratio of polyanion to conductive polymer,D50 is average particle size. Example 1-2, utilizing a higher charge(133,000 μFV/g) part type demonstrated the highest capacitance recoveryand lowest ESR even though the slurry had the lowest conductivity forthe PSSA samples. Its improvement in capacitance cannot be completelyattributed to low average particle size, as Example C-3 had even loweraverage particle size but the capacitance improvement over Example I-1was minimum. As illustrated in FIGS. 4 and 5 the correlation betweencapacitance and ESR vs. polyanion/PEDOT weight ratio is contrary to theexpectations in the art as expressed in U.S. Published Pat. Appl. No.2015/0279503. Also, as illustrated in FIG. 3, as PSSA/PEDOT weight ratioincreases conductivity decreases. Better ESR achieved with conductivepolymer dispersion having lower conductivity is contradictory to commonunderstanding of ESR-conductivity correlation.

A particular advantage is in capacitance recovery, or Cap recovery,which for a powder charge in excess of 100,000 μFV/g a Cap recovery ofat least 65% can be achieved. With a powder charge in excess of 65,000μFV/a, Cap recovery of at least 70% can be achieved. With a charge inexcess of 45,000 μFV/a, Cap recovery of greater 75% can be achieved.

Cap recovery could be higher if in-situ or soluble conductive polymerprecursor such as S1 or S2 are applied in case of Table 2 and Table 3based on result presented in Table 4.

The same trends are observed with conductive polymer dispersion madewith polystyrene-polystyrene sulfonic acid (ST) as a dopant. Thedispersion with the highest polyanion/PEDOT ratio, Example I-3 wasobserved to have the best capacitance and ESR, even though theconductivity was only about 94 S/cm. On the contrary, for a lower charge(13,000 μFV/g) powder, Example I-7 showed very little improvement incapacitance and ESR over Example C-8. The results presented in Table 1demonstrate that a first conductive polymer layer having a weight ratioof polyanion to conductive polymer of greater than 3 and an averageparticle size of less than 20 nm average diameter (D50) is applied to ahigh charge capacitor the electrical properties are improved.

TABLE 2 Samples Ratio Capacitance Recovery % ESR (mΩ) BDV/Vf I-4 5 70.4102.9 1.90 C-6 2.5 12.8 143.9 1.68

Table 2 demonstrates the advantages of the invention with another highercharge (65,000 μFV/g) powder and the ability to achieve a breakdownvoltage (BDV)/formation voltage (Vf) ratio in excess of 1.

TABLE 3 Capacitance ESR Power Cycling Cap Change Samples Ratio Recovery% (mΩ) after 60,000 cycles % I-5 3.3 74.2 31.1  −9.4% I-6 5 73.6 29.8 −2.7% C-7 2.5 70.9 33.2 −28.3%

Table 3 illustrates the invention for a 48,000 μFV/g charge power.Higher PSSA/PEDOT ratios only showed slightly better ESR and capacitancethan C-7. Even though the capacitance benefit was not very significant,power cycling capacitance change showed that higher PSSA/EDOT ratio isadvantageous for retaining the initial capacitance. As can be realizedfrom the data provided in Table 3, a power cycling Cap reduction of lessthan 10% after 60,000 cycles can be achieved and, even more preferably,less than 5%.

TABLE 4 First Precursor Conductive Capacitance Samples Polymer PolymerRatio Recovery % ESR (mΩ) I-8 S1 PEDOT-PSSA 3.3 32.6 260.0 I-9 S1PEDOT-PSSA 5 59.3 152.4 C-9 S1 PEDOT-PSSA 2.5 10.2 326.3 C-10 S1 None na13.4 2319.3 I-10 None S2/PEDOT-PSSA 5 65.3 126.8 (1:9) C-11 S2 None na22.4 200.4 I-1 None PEDOT-PSSA 3.3 15.5 146.0 I-2 None PEDOT-PSSA 5 49.9119.1

The results presented in Table 4 demonstrate that other conductivepolymers such as in-situ PEDOT (without polyanion) and soluble PEDOT orother conductive polymers without polyanion can be applied as aprecursor conductive polymer before the first slurry and second slurry.In Table 4, two layers of self-doped PEDOT solution (S1) were appliedbefore the first slurry. The highest capacitance and lowest ESR wasrealized when the self-doped conductive polymer (S1) is followed by adispersion having a weight ratio of polyanion to conductive polymer ofabout 5. A synergy is realized when the conductive polymer dispersionwith the polyanion/conductive polymer weight ratio greater than 3 iscombined with the soluble conductive polymer (S1). Mixing anotherconductive polymer solution (S2) with the conductive polymer dispersionhaving a high polyanion to conductive polymer weight ratio alsogenerated similar benefit as shown by Example I-10 and C-11. Reversingthe application order by dipping in the conductive polymer dispersionfirst followed by a conductive polymer solution could also offer similarbenefit for capacitance.

TABLE 5 Capacitance ESR DCL Examples D50 (nm) Recovery % (mΩ) (μA)BDV/Vf I-11 16.4 80.1 50.7 4.0 1.01 C-12 15.5 76.2 47.0 7.7 0.87

The results presented in Table 5 illustrate that by adding silanecoupling agent and epoxy compounds into the first slurry thecapacitance, leakage and breakdown voltage (BDV) can be improved.Alternatively, the additives can be applied as a separate solution fromthe first slurry and still achieve similar performance enhancement.Without being limited to theory, it is hypothesized that the epoxycompound may form a complex with the conductive polymer dispersions andincreased the conductive particle size by having a thicker insulativelayer around the conductive core. This was confirmed by increase inparticle diameter D50. Despite the particle size increase, theinsulative additives had positive effect on impregnation and covering ofthe anode pores. The silane coupling agent may also increase theadhesion between the first conductive polymer and the dielectric.

The invention has been described with reference to the preferredembodiments without limit thereto. One of skill in the art would realizeadditional embodiments and improvements which are not specifically setforth herein but which are within the scope of the invention as morespecifically set forth in the claims appended hereto.

Claimed is:
 1. A process for forming an electrolytic capacitorcomprising: providing an anode comprising a dielectric thereon whereinsaid anode comprises a sintered powder wherein said powder has a powdercharge of at least 45,000 μFV/g; and forming a first conductive polymerlayer encasing at least a portion of said dielectric by applying a firstslurry wherein said first slurry comprises a polyanion and a conductivepolymer and wherein said polyanion and said conductive polymer are in aweight ratio of greater than 3 wherein said conductive polymer and saidpolyanion forms conductive particles with an average particle size of nomore than 20 nm.
 2. The process for forming an electrolytic capacitor ofclaim 1 wherein said first slurry has a conductivity of no more than 200S/cm.
 3. The process for forming an electrolytic capacitor of claim 1wherein said weight ratio is no more than
 10. 4. The process for formingan electrolytic capacitor of claim 3 wherein said weight ratio is nomore than
 6. 5. The process for forming an electrolytic capacitor ofclaim 1 wherein said electrolytic capacitor exhibits a breakdownvoltage/formation voltage ratio of greater than
 1. 6. The process forforming an electrolytic capacitor of claim 1 wherein said first slurryis prepared by a rotor-stator mixing device followed by homogenization.7. The process for forming an electrolytic capacitor of claim 1 whereinsaid anode comprises a valve metal selected from the group consisting ofAl, W, Ta, Nb, Ti, Zr and Hf.
 8. The process for forming an electrolyticcapacitor of claim 7 wherein said anode comprises a valve metal selectedfrom the group consisting of niobium, aluminum, tantalum and NbO.
 9. Theprocess for forming an electrolytic capacitor of claim 8 wherein saidanode comprises a tantalum.
 10. The process for forming an electrolyticcapacitor of claim 1 further comprising forming a subsequent conductivepolymer layer on said first conductive polymer layer.
 11. The processfor forming an electrolytic capacitor of claim 10 wherein said formingof said subsequent conductive polymer layer comprises applying a secondslurry wherein said second slurry comprises a second polyanion and asecond conductive polymer.
 12. The process for forming an electrolyticcapacitor of claim 11 wherein said second polyanion and said secondconductive polymer are in a weight ratio of less than
 3. 13. The processfor forming an electrolytic capacitor of claim 11 wherein said secondslurry has a higher conductivity than said first slurry.
 14. The processfor forming an electrolytic capacitor of claim 1 wherein said conductiveparticles further comprise an insulative compound.
 15. The process forforming an electrolytic capacitor of claim 14 wherein said insulativecompound comprises at least one of a silane compound or an epoxycompound.
 16. The process for forming an electrolytic capacitor of claim14 wherein said insulative compound comprises at least one of a silanecompound, an epoxy compound or an ionic liquid.
 17. The process forforming an electrolytic capacitor of claim 1 wherein said first slurrycomprises at least one ionic liquid.
 18. The process for forming anelectrolytic capacitor of claim 1 wherein said conductive polymercomprises a conductive polymer selected from the group consisting ofpolyaniline, polypyrrole, polythiophene and their derivatives.
 19. Theprocess for forming an electrolytic capacitor of claim 18 wherein saidconductive polymer is selected from the group consisting ofpoly(3,4-ethylenedioxythiophene),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulphonicacid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole),poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole),poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole),poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole),poly(3-methyl-4-carboxyethylpyrrole),poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole),poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene),poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene),poly(3-decylthiophene), poly(3-dodecylthiophene),poly(3-octadecylthiaphene), poly(3-bromothiophene),poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene),poly(3-hydroxythiophene), poly(3-methoxythiophene),poly(3-ethoxythiophene), poly(3-butoxythiophene),poly(3-hexyloxythiophene), poly(3-heptyloxythiophene),poly(3-octyloxythiophene), poly(3-decyloxythiophene),poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene),poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene),poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene),poly(3,4-butenedioxythiophene), poly(3-carboxythiophene),poly(3-methyl-4-carboxythiophene),poly(3-methyl-4-carboxyethylthiophene),poly(3-methyl-4-carboxybutylthiophene), polyaniline,poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), and poly(3-aniline sulfonate).
 20. The process for formingan electrolytic capacitor of claim 19 wherein said conductive polymer ispoly(3,4-ethylenedioxythiophene).
 21. The process for forming anelectrolytic capacitor of claim 1 wherein said polyanion comprises atleast one of a styrene sulfonic acid group or a styrene sulfonate group.22. The process for forming an electrolytic capacitor of claim 1 whereinsaid polyanion is defined by Formula A:A_(x)B_(y)C_(z)  Formula A wherein: A is polystyrenesulfonic acid orsalt of polystyrenesulfonate; B and C separately represent polymerizedunits substituted with a group selected from: -carboxyl groups; —C(O)OR⁶wherein R⁶ is selected from the group consisting of: an alkyl of 1 to 20carbons optionally substituted with a functional group selected from thegroup consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide,imide, thiol, alkene, alkyne, azide, phosphate, acrylate, anhydride and—(CHR⁷CH₂O)_(b)-R⁸ wherein: R⁷ is selected from a hydrogen or an alkylof 1 to 7 carbons b is an integer from 1 to the number sufficient toprovide a molecular weight of up to 200,000 for the —CHR⁷CH₂O— group;and R⁸ is selected from the group consisting of hydrogen, silane,phosphate, acrylate, an alkyl of 1 to 9 carbons optionally substitutedwith a functional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate, and anhydride; —C(O)—NHR⁹ wherein: R⁹ ishydrogen or an alkyl of 1 to 20 carbons optionally substituted with afunctional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate and anhydride; —C₆H₄—R¹ wherein: R¹⁰ isselected from: a hydrogen or alkyl optionally substituted with afunctional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate and anhydride; a reactive group selected fromthe group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide,amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride and—(O(CHR¹¹CH₂O)_(d)—R¹² wherein: R¹¹ is a hydrogen or an alkyl of 1 to 7carbons; d is an integer from 1 to the number sufficient to provide amolecular weight of up to 200,000 for the —CHR¹¹CH₂O— group; R¹² isselected from the group consisting of hydrogen, an alkyl of 1 to 9carbons optionally substituted with a functional group selected from thegroup consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide,imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride;—C₆H₄—O—R¹³ wherein: R¹³ is selected from: a hydrogen or an alkyloptionally substituted with a reactive group selected from the groupconsisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide,thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; areactive group selected from the group consisting of epoxy, silane,alkene, alkyne, acrylate, phosphate and —(CHR¹⁴CH₂O)_(e)—R¹⁵ wherein:R¹⁴ is a hydrogen or an alkyl of 1 to 7 carbons; e is an integer from 1to the number sufficient to provide a molecular weight of up to 200,000for the —CHR¹⁴CH₂O— group; and R¹⁵ is selected from the group consistingof hydrogen and an alkyl of 1 to 9 carbons optionally substituted with afunctional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,azide, acrylate, phosphate and anhydride; and x, y and z, taken togetherare sufficient to form a polyanion with a molecular weight of at least100 to no more than 500,000 and y/x is 0.01 to 100; z is 0 to a ratioz/x of no more than 100; y represents 1 to 50% and z represents 0 to 49%of the sum total of x+y+z.
 23. The process for forming an electrolyticcapacitor of claim 22 wherein R⁷ is selected the group consisting ofhydrogen and methyl.
 24. The process for forming an electrolyticcapacitor of claim 22 wherein R¹¹ is selected the group consisting ofhydrogen and methyl.
 25. The process for forming an electrolyticcapacitor of claim 22 wherein R¹⁴ is selected the group consisting ofhydrogen and methyl.
 26. The process for forming an electrolyticcapacitor of claim 22 wherein x represents 50-99%; y represents 10 to30% and z represents 0 to 20%.
 27. The process for forming anelectrolytic capacitor of claim 26 wherein x represents 70-90%.
 28. Theprocess for forming an electrolytic capacitor of claim 1 furthercomprising forming a precursor conductive layer prior to said forming ofsaid first conductive polymer layer.
 29. The process for forming anelectrolytic capacitor of claim 28 wherein said forming of saidprecursor conductive layer comprises in-situ polymerization.
 30. Theprocess for forming an electrolytic capacitor of claim 28 wherein saidforming of said precursor conductive layer comprises coating a solubleconductive polymer solution.
 31. The process for forming an electrolyticcapacitor of claim 30 wherein said precursor conductive layer does notcomprise polyanion.
 32. The process for forming an electrolyticcapacitor of claim 30 further comprising crosslinking said solubleconductive polymer.
 33. The process for forming an electrolyticcapacitor of claim 1 wherein said capacitor has a capacitance recoveryof at least of at least 65%.
 34. The process for forming an electrolyticcapacitor of claim 33 wherein said capacitor has a capacitance recoveryof at least of at least 70%.
 35. The process for forming an electrolyticcapacitor of claim 34 wherein said capacitor has a capacitance recoveryof at least of at least 75%.
 36. The process for forming an electrolyticcapacitor of claim 1 wherein said capacitor has a capacitance reductionof less than 5% after 60,000 cycles of power cycling at rated voltage.37. The process for forming an electrolytic capacitor of claim 36wherein said capacitor has a capacitance reduction of less than 10%after 60,000 cycles of power cycling at rated voltage.
 38. Anelectrolytic capacitor comprising: an anode comprising a dielectricthereon wherein said anode comprises a sintered powder wherein saidpowder has a powder charge of at least 45,000 μFV/g; and a firstconductive polymer layer encasing at least a portion of said dielectricwherein said first conductive polymer comprises a polyanion and aconductive polymer and wherein said polyanion and said conductivepolymer are in a weight ratio of greater than 3 wherein said conductivepolymer and said polyanion are conductive particles having an averageparticle size of no more than 20 nm.
 39. The electrolytic capacitor ofclaim 38 wherein said weight ratio is no more than
 10. 40. Theelectrolytic capacitor of claim 39 wherein said weight ratio is no morethan
 6. 41. The electrolytic capacitor of claim 38 having a breakdownvoltage/formation voltage ratio of greater than
 1. 42. The electrolyticcapacitor of claim 38 wherein said anode comprises a valve metalselected from the group consisting of Al, W, Ta, Nb, Ti, Zr and Hf. 43.The electrolytic capacitor of claim 42 wherein said anode comprises avalve metal selected from the group consisting of niobium, aluminum,tantalum and NbO.
 44. The electrolytic capacitor of claim 43 whereinsaid anode comprises tantalum.
 45. The electrolytic capacitor of claim38 wherein said conductive polymer particles comprise an insulativecompound.
 46. The electrolytic capacitor of claim 45 wherein saidinsulative compound comprises a silane compound or an epoxy compound.47. The electrolytic capacitor of claim 45 wherein said insulativecompound comprises at least one ionic liquid.
 48. The electrolyticcapacitor of claim 38 further comprising a subsequent conductive polymerlayer on said first conductive polymer layer.
 49. The electrolyticcapacitor of claim 48 wherein said subsequent conductive polymer layercomprises a second polyanion and a second conductive polymer.
 50. Theelectrolytic capacitor of claim 49 wherein said second polyanion andsaid second conductive polymer are in a weight ratio of less than
 3. 51.The electrolytic capacitor of claim 38 wherein said conductive polymercomprises a conductive polymer selected from the group consisting ofpolyaniline, polypyrrole, polythiophene and their derivatives.
 52. Theelectrolytic capacitor of claim 51 wherein said conductive polymer isselected from the group consisting of poly(3,4-ethylenedioxythiophene),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulphonicacid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole),poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole),poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole),poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole),poly(3-methyl-4-carboxyethylpyrrole),poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole),poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene),poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene),poly(3-decylthiophene), poly(3-dodecylthiophene),poly(3-octadecylthiophene), poly(3-bromothiophene),poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene),poly(3-hydroxythiophene), poly(3-methoxythiophene),poly(3-ethoxythiophene), poly(3-butoxythiophene),poly(3-hexyloxythiophene), poly(3-heptyloxythiophene),poly(3-octyloxythiophene), poly(3-decyloxythiophene),poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene),poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene),poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene),poly(3,4-butenedioxythiophene), poly(3-carboxythiophene),poly(3-methyl-4-carboxythiophene),poly(3-methyl-4-carboxyethylthiophene),poly(3-methyl-4-carboxybutylthiophene), polyaniline,poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), and poly(3-aniline sulfonate).
 53. The electrolyticcapacitor of claim 52 wherein said conductive polymer ispoly(3,4-ethylenedioxythiophene).
 54. The electrolytic capacitor ofclaim 52 wherein said polyanion comprises at least one of a styrenesulfonic acid group or a styrene sulfonate group.
 55. The electrolyticcapacitor of claim 38 wherein said polyanion is defined by Formula A:A_(x)B_(y)C_(z)  Formula A wherein: A is polystyrenesulfonic acid orsalt of polystyrenesulfonate; B and C separately represent polymerizedunits substituted with a group selected from: -carboxyl groups; —C(O)OR⁶wherein R⁶ is selected from the group consisting of: an alkyl of 1 to 20carbons optionally substituted with a functional group selected from thegroup consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide,imide, thiol, alkene, alkyne, azide, phosphate, acrylate, anhydride and—(CHR⁷CH₂O)_(b)-R⁸ wherein: R⁷ is selected from a hydrogen or an alkylof 1 to 7 carbons b is an integer from 1 to the number sufficient toprovide a molecular weight of up to 200,000 for the —CHR⁷CH₂O— group;and R⁸ is selected from the group consisting of hydrogen, silane,phosphate, acrylate, an alkyl of 1 to 9 carbons optionally substitutedwith a functional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate, and anhydride; —C(O)—NHR⁹ wherein: R⁹ ishydrogen or an alkyl of 1 to 20 carbons optionally substituted with afunctional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate and anhydride; —C₆H₄—R¹ wherein: R¹⁰ isselected from: a hydrogen or alkyl optionally substituted with afunctional group selected from the group consisting of hydroxyl,carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne,phosphate, azide, acrylate and anhydride; a reactive group selected fromthe group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide,amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride and—(O(CHR¹¹CH₂O)_(d)—R¹² wherein: R¹¹ is a hydrogen or an alkyl of 1 to 7carbons; d is an integer from 1 to the number sufficient to provide amolecular weight of up to 200,000 for the —CHR¹¹CH₂O— group; R¹² isselected from the group consisting of hydrogen, an alkyl of 1 to 9carbons optionally substituted with a functional group selected from thegroup consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide,imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride;—C₆H₄—O—R¹³ wherein: R¹³ is selected from: a hydrogen or an alkyloptionally substituted with a reactive group selected from the groupconsisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide,thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; areactive group selected from the group consisting of epoxy, silane,alkene, alkyne, acrylate, phosphate and —(CHR¹⁴CH₂O)_(e)—R¹⁵ wherein:R¹⁴ is a hydrogen or an alkyl of 1 to 7 carbons; e is an integer from 1to the number sufficient to provide a molecular weight of up to 200,000for the —CHR¹⁴CH₂O— group; and <R¹⁵ is selected from the groupconsisting of hydrogen and an alkyl of 1 to 9 carbons optionallysubstituted with a functional group selected from the group consistingof hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol,alkene, alkyne, azide, acrylate, phosphate and anhydride; and x, y andz, taken together are sufficient to form a polyanion with a molecularweight of at least 100 to no more than 500,000 and y/x is 0.01 to 100; zis 0 to a ratio z/x of no more than 100; y represents 1 to 50% and zrepresents 0 to 49% of the sum total of x+y+z.
 56. The electrolyticcapacitor of claim 55 wherein R⁷ is selected the group consisting ofhydrogen and methyl.
 57. The electrolytic capacitor of claim 55 whereinR¹¹ is selected the group consisting of hydrogen and methyl.
 58. Theelectrolytic capacitor of claim 55 wherein R¹⁴ is selected the groupconsisting of hydrogen and methyl.
 59. The electrolytic capacitor ofclaim 55 wherein x represents 50-99%; y represents 10 to 30% and zrepresents 0 to 20%.
 60. The electrolytic capacitor of claim 59 whereinx represents 70-90%.
 61. The electrolytic capacitor of claim 38 furthercomprising a precursor conductive layer prior between said firstconductive polymer layer and said dielectric.
 62. The electrolyticcapacitor of claim 61 wherein said precursor conductive layer does notcomprise polyanion.
 63. The electrolytic capacitor of claim 61 whereinsaid precursor conductive layer is crosslinked.
 64. The electrolyticcapacitor of claim 38 wherein said capacitor has a capacitance recoveryof at least of at least 65%.
 65. The electrolytic capacitor of claim 64wherein said capacitor has a capacitance recovery of at least of atleast 70%.
 66. The electrolytic capacitor of claim 65 wherein saidcapacitor has a capacitance recovery of at least of at least 75%. 67.The electrolytic capacitor of claim 38 wherein said capacitor has acapacitance reduction of less than 5% after 60,000 cycles of powercycling at rated voltage.
 68. The electrolytic capacitor of claim 67wherein said capacitor has a capacitance reduction of less than 10%after 60,000 cycles of power cycling at rated voltage.